Patent GB-642930-A (GB)
Title: Improvements in or relating to nitriles and method of preparing same
Inventor: NIEDERHAUSER WARREN D
IPC: C07C255/32
Filed: 1948-01-01
Abstract: Nitriles of the formula Ar-R-CN, where Ar is an aromatic hydrocarbon radical and R is an alkylene group (straight or branched-chain) containing 10 to 21 carbon atoms, are used as plasticizers for thermoplastic materials such as nitrocellulose, cellulose acetate, propionate and butyrate, ethyl and benzyl cellulose, polyvinyl chloride and acetate and co-polymers thereof, and polyvinyl acetals such as the formal and butyral.  The radical Ar in the above formula preferably has 6 to 14 carbon atoms, and a number of radicals of the benzene and naphthalene series are specified, including biphenyl and dibenzyl.  In an example, polyvinyl chloride, basic lead carbonate, stearic acid and either tolyl-stearonitrile or biphenyl-stearonitrile are milled together, and the properties of the composition compared with those of a similar composition using dioctyl phthalate as plasticizer.ALSO:Nitriles of the formula Ar-R-CN, where Ar is an aromatic hydrocarbon radical and R is an alkylene group containing 10 to 21 carbon atoms, are prepared by (1) reacting ammonia with an aliphatic monocarboxylic acid having one olefinic bond in a radical containing the same number of carbon atoms as R or an ester of such acid in the presence of a dehydrating agent to form an unsaturated nitrile, and reacting the latter with an aromatic hydrocarbon ArH by a Friedel-Crafts reaction in the presence of aluminium chloride, or (2) reacting an aromatic hydrocarbon ArH with an acid or ester as defined above by a Friedel-Crafts reaction in the presence of aluminium chloride, and reacting the product with ammonia in the presence of a dehydrating agent at an elevated temperature.  The Friedel-Craft reaction is in each case conducted below 90 DEG  C., and preferably below 85 DEG  C.  The radical Ar preferably has 6-14 carbon atoms, e.g. phenyl, tolyl, xylyl, naphthyl, biphenyl, dibenzyl, benzylphenyl, ethyl-phenyl, isopropyl-phenyl, trimethyl-phenyl, di-isopropyl-phenyl, tert.-amyl-phenyl and methyl-naphthyl.  The group R in the product may be represented by the formula -(CnH2n) and may be straight- or branched-chain.  The acids or esters used as starting materials may be obtained from vegetable or fish oils or may be synthesised; specified acids are D 10-undecenoic, D 11-dodecenoic, D 12-tridecenoic, oleic, myristoleic, palmitolenic, elaidic, iso-oleic, petroselic, D 11-and D 12-octadecenoic, erucic, cetoleic and brassidic.  The acids or their lower alkyl esters may be converted into the corresponding nitriles by heating them to 250-350 DEG  C. with a dehydrating agent (e.g. ammonium molybdate, alumina or thoria) and passing ammonia through the molten mass.  Examples show the reaction of oleonitrile (obtained from oleic acid and ammonia) with toluene, benzene, m-xylene, 1 : 3 : 5-trimethylbenzene, isopropyl-benzene, naphthalene, diphenyl, and a mixture of a - and b -methylnaphthalene; also of undecylenonitrile and eruconitrile with toluene.  Further examples show the preparation of tolyl-stearic acid from toluene and oleic acid and of xylyl-stearic acid methyl ester from m-xylene and methyl oleate; these acids are converted into the nitriles by treatment with ammonia.  According to the Specification as open to inspection under Sect. 91, nitriles of the above formula may be made directly by reacting the aromatic hydrocarbon, ammonia and the olefinic acid or an ester thereof.  This subject-matter does not appear in the Specification as accepted.